Dyeing of synthetic organic material with aliphatic and halogenated aliphatic solution

ABSTRACT

A process for the dyeing of synthetic organic material is described, the said process comprising the discontinuous or continuous dyeing, at temperatures preferably above 120*C, of said material from a dye liquor consisting of 20 to 75 per cent by weight of a water-insoluble, aliphatic or cycloaliphatic hydrocarbon having at least 8 carbon atoms, and 80 to 25 per cent by weight of a polyhalogenated, lower alphatic hydrocarbon boiling between 70* and 180*C, and at least one advantageously finely divided dispersion dyestuff, and optionally further additives; and, optionally, the subsequent rinsing and drying of the dyed synthetic organic material, whereby deeply coloured dyeings are obtained which are even and fast to light, wetprocessing, sublimation and rubbing even on poorly absorbing material.

United States Patent 11 1 Hoster et a1.

1 1 DYEING OF SYNTHETIC ORGANIC MATERIAL WITH ALIPHATIC AND HALOGENATED ALIPHATIC SOLUTION [75] Inventors: Hansruedi Hoster. Dornach; Jurgen Markert, Basel. both of Switzerland [73] Assignee: Ciba-Geigy AG, Basel. Switzerland [221 Filed: Apr. 10, 1973 [211 Appl. No.: 349,893

[] Foreign Application Priority Data Apr. 12. 1972 Switzerland 5356/72 [52] US. Cl. 8/174; 8/175; 8/94 [51] Int. Cl.' D06P 1/68 [58] Field 01' Search 8/94. 174. 175

[56] Reterences Cited UNITED STATES PATENTS 1.925.602 9/1933 Pitman 23/250 2.492.048 12/1949 Klabundle 260/6525 2.828.180 3/1958 Sertorio 8/174 X 3.040.108 6/1962 Campbell 260/6525 3.046.076 7/1962 Upshur 8/173 3.523.749 8/1970 MacLeod et a1... 8/174 X 3.758.272 9/1973 Datye et a1. 8/174 X 3.792.971 2/1974 Neeff et a1. 8/174 X 3.807.953 4/1974 Baumann 8/175 3.822.992 7/1974 Hederich et a1. 8/174 X FOREIGN PATENTS OR APPLICATIONS 2.032.391 2/1970 France 1 Nov. 11, 1975 504.558 9/1938 United Kingdom 1.045.839 10/1966 United Kingdom 1.192.984 9/1966 United Kingdom 1.333.722 10/1973 United Kingdom 1.603.051 4/1971 France 72/3918 6/1972 South Africa /3050 5/1969 South Africa Primary E.\'amt'ner-Samuel Feinberg Assistant Swimmer-P. Av Nelson Attorney, Agent. or Firm-Joseph G. Kolodny'. Edward McC. Roberts; Prabodh l. Almaula [5 7] ABSTRACT A process for the dyeing of synthetic organic material is described. the said process comprising the discontinuous or continuous dyeing. at temperatures preferably above 120C. of said material from a dye liquor consisting of 20 to 75 per cent by weight of a waterinsoluble. aliphatic or cycloaliphatic hydrocarbon having at least 8 carbon atoms. and to 25 per cent by weight of a polyhalogenated. lower alphatic hydrocarbon boiling between 70 and C. and at least one advantageously finely divided dispersion dyestuff. and optionally further additives; and. optionally. the subse quent rinsing and drying of the dyed synthetic organic material. whereby deeply coloured dyeings are ob tained which are even and fast to light. wetprocessing. sublimation and rubbing even on poorly absorbing material.

20 Claims. N0 Drawings DYEING OF SYNTHETIC ORGANIC MATERIAL WITH ALIPHATIC AND I'IALOGENATED ALIPl-IATIC SOLUTION The present invention relates to a process for the dyeing of synthetic organic material, particularly textile material, from organic dye liquors, to the organic dye liquors usable in this process, as well as to the material dyed by this process.

Various suggestions have already been made for the dyeing of natural and synthetic textile material from organic solvents or solvent mixtures. It is the usual practice in this connection to use a solution of the dyestuff(s) in an organic dye bath.

Since the exhaustion of the dye bath with application of solutions of dyestuffs in organic solvents or solvent mixtures is mostly inadequate, it has also been suggested that during the dyeing process water or a solvent that lowers the solubility of the dyestuff in the solvent or solvent mixture be slowly added. This process is however complicated.

With the use of apolar solvents, particularly the noncombustible, halogenated, aliphatic hydrocarbons, only a limited number of dyestuffs are applicable, because most dyestuffs have too low a solubility in these solvents. It has therefore been suggested for the dyeing of fibre material from organic solvents by the exhaust process that the fibre materials be dyed with solutions of anionic dyestuffs in organic solvents not miscible with water, in which solvents the dyestuff is dispersed or solubilised by means of a surfaceactive agent. These processes have the disadvantage that, for example, the anionic dyestuffs, particularly on natural polyamide, have insufficient affinity, and that the dyeings obtained in this manner possess inadequate fastness properties, the dyeings having, in particular, poor fastness to perspiration and to washing.

There is known from the Swiss Pat. Specification No. 503,785, Examples 1 and 5, a process for the dyeing of polyester of polyamide textile material by the use of dye baths which are obtained by the addition, e.g. to perchloroethylene, of dyestuff preparations consisting of, among other things, dispersion dyestuff ground in paraffin oil. The exhaustion of these dye baths containing up to a maximum of 5 per cent by weight of paraffin oil is however insufficient.

A process has now been discovered which renders possible the dyeing of synthetic organic material from organic dye liquors, even with the use of solutions of dyestuffs in organic solvent, with good to excellent exhaustion of the bath.

The new process comprises the discontinuous or continuous dyeing, at temperatures of above 100C, preferably above 120C, of the synthetic organic material from a dye liquor consisting of to 75, advantageously 50 to 70, per cent by weight of a water-insoluble, aliphatic or cycloaliphatic hydrocarbon having at least 8 carbon atoms, and 80 to 25, advantageously 50 to 30, per cent by weight of a polyhalogenated, lower aliphatic hydrocarbon boiling between 70 and 180C, and at least one advantageously finely divided dispersion dyestuff, and possible further additives; and, optionally, the subsequent rinsing and drying of the dyed synthetic organic material.

Surprisingly, there are obtained, especially within the stated mixture limits, with good to excellent exhaustion of the bath, deeply coloured, even and fast dyeings,

particularly dyeings fast to light, wet processing, sublimation and rubbing, even on poorly absorbing material. With the application of amounts of paraffin oil smaller or larger than the given amounts, the exhaustion of the bath is appreciably less favourable. The fastness to wet processing exhibited by the thus obtained very even dyeings, well dyed throughout, corresponds, also in the dyeing of wound packages, such as, e.g. cheeses, to that of dyeings obtained with dispersion dyestuffs from an aqueous bath.

Suitable water-insoluble, aliphatic and cycloaliphatic hydrocarbons usable according to the invention, having at least 8 carbon atoms, are, for example, the following: both straight-chain and branched alkanes, advantageously having 12 to 25 carbon atoms; cycloalkanes such as, e.g. ethylcyclohexane, cyclooctane, cyclodecane or Decalin; halogenation products of higher molecular hydrocarbons which, for example, are obtained by addition of chlorine to hard paraffin; oxygen-containing waxes, e.g. the mixtures (forming by atmospheric oxidation of aliphatic hydrocarbons) of esters, acids and oxyacids of the corresponding higher molecular hydrocarbons; also aliphatic hydrocarbons of which the carbon chain is interrupted by hetero atoms, particularly by -O-, -S- or NI-L, such as, e.g. di-n-octyl ether, di-n-decyl-thio ether or di-n-dodecylamine.

it is advantageous to use higher molecular mixtures of aliphatic hydrocarbons that are obtained inter alia from the liquid fractions in the production of paraffin, e.g. the petroleum fraction of mineral oil containing the paraffins C, C and boiling within the range of 220 to 270C, or gas oil fractions also containing solid hydrocarbons having up to about 25 carbon atoms.

Particularly suitable are the high-boiling ligroin or petroleum fractions obtainable under the designation of Schwerbenzin, Kerosin and especially "Paraffinol (heavy petrol, kerosene and paraffin oil). Heavy petrol contains ca. 20 to 25 percent of fractions boiling at 100C, the remainder mostly at I50 l80C, occasionally even higher. Kerosene is the distillate passing over after the ligroin fraction; it has a boiling range of I 288C and a density of 0.7 to 0.8, and consists essentially of a hydrocarbon mixture of C to C Finally, paraffin oil consists of a higher molecular mixture of aliphatic hydrocarbons obtained from the liquid fractions in the obtaining of paraffin, and having a boiling point of at least 280C and a density of at least 0.75.

It is advantageous to employ water-insoluble, aliphatic and cycloaliphatic hydrocarbons of which the boiling point is at least equal to, particularly, however, higher to appreciably higher than, that of the also employed polyhalogenated lower aliphatic hydrocarbon according to the invention.

Suitable polyhalogenated, lower aliphatic hydrocarbons boiling between 70 and 180C for the process according to the invention are, for example: carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, trichlorotrifluoroethane, dibromoethylene, dichloropropane, trichloropropane, pentachloropropane, dichlorobutane a'nd dichlorohexane. Particularly advantageous are chlorinated hydrocarbons boiling between and C, such as trichloroethylene, l,l,l-trichloroethane, and especially tetrachloroethylene (perchloroethylene").

In order to stabilise the pH-value of commercial tetrachloroethylene, small amounts are in many cases added to it of aliphatic, cycloaliphatic, aromatic or heterocyclic amines, such as, e.g. triethylamine, aniline,

pyridine, picoline, N-methylpyrrolidone or other derivatives. With the employment of such stabilised tetrachloroethylene for the dyeing of synthetic organic material according to the present invention, there occurs, however, a noticeable grey discolouration of the material and consequently a distinct dulling of the dyeing. It has now been found that this disadvantageous effect on the material can be avoided by the addition of small amounts of anti-oxidants to the tetrachloroethylene stabilised with the mentioned amines.

Applicable anti-oxidants are all the important classes of compounds having an anti-oxidising action, such as, e.g.:

a. the derivatives of alkylated, arylated or mixed phenols, phenol ethers or phenol esters, as well as bisphenols with or without alkylene bridging, particularly those of the general formula wherein R represents an alkyl group having I to 6 carbon atoms, an aryl or an alkylaryl group, and n denotes the numbers to 6;

b. hydroquinone and its functional derivatives, such as hydroquinone-monoand dialkyl of arylalkyl ethers;

c. the esters of gallic acid or citraconic acid, as well as mixtures thereof;

d. dialkylphosphonates, particularly those with sterically inhibited phenols, or also p-hydroxyphenylphosphonates and compounds of p-phenylenediamine or of p-aminophenol;

e. organic sulphur compounds having an oxidationinhibiting action, and

f. compounds of the formamidinesulphinic acid type or inorganic complex hydrides such as NaBl-L, etc., of which the hydrogen can be partially replaced by organic radicals, such as NaBI-KOCHQ; or NaBH- (OC,H Preferred antioxidants, since they are effective in extremely small amounts, are those which are sufficiently soluble in the mixture ratios of tetrachloroethylene and paraffin oil according to the invention.

The chemical constitution of the given anti-oxidants can be found in Kirk-Othmer, "Encyclopedia of Chemical Technology," 2nd Edition, Vol. 2, pages 588-604 (I963).

The quantity ratios of the employed anti-oxidants can vary within wide limits; in general, amounts of 0.00] to 5 g/l of dye liquor, particularly 0.01 to 1.0 g/l, have proved effective.

The dispersion dyestuffs usable according to the invention can belong to the most diverse classes of dyestuffs. They are, in particular, azo, anthraquinone, nitro, phthalocyanine, methine, styryl, naphthoperinone, quinophthalone, acridone or 5-amino-8-hydroxyl-l,4- naphthoquinoneimine dyestuffs. Preferred dyestuffs are metal-free monoor disazo dyestuffs, nitro dyestuffs, methine dyestuffs and anthraquinone dyestuffs.

By dyestuffs are meant also optical dispersion brighteners, e.g. brighteners from the coumarin, azole or naphthalamide series.

The amounts in which the dispersion dyestuffs are used in the organic dye baths according to the inven- 4 tion can vary, depending on the desired depth of colour, within wide limits; in general, amounts of from 0.001 to 10 per cent by weight, relative to the material to be dyed, of one or more of the stated dyestuffs have proved advantageous.

If dispersion dyestuffs soluble in boiling perchloroethylene are used, then the commercial dyestuffs containing no dispersing agents can be employed direct. If the dyestuffs are at least partially in the dispersed state in the organic dye liquor, then the presence of dispersing agents is advisable.

Advantageously, dispersion dyestuffs are used which are difficulty soluble in boiling perchloroethylene and which contain a dispersing agent soluble in polyhalogenated lower aliphatic hydrocarbon, but which does not solubilise the dispersion dyestuff. Particularly preferred dispersion dyestuffs are ones which have a solubility in boiling perchloroethylene of at most 0.05, preferably 0.03, per cent by weight, and a particle size of at most 5 1., preferably one between 0.1 and 3 u.

The finely divided dispersion dyestuffs can be obtained by known processes; for example, by mechanical particle-size reduction of the dyestuff together with a dispersing agent, and optionally smallish amounts of halogenated aliphatic hydrocarbon, particularly perchloroethylene, e.g. in a kneading apparatus, preferably however in a grinding mill. Especially suitable for this purpose are ball or sand mills.

Suitable dispersing agents are commercial anionic, cationic, ampholytic and, in particular, nonionic surface-active agents which advantageously are soluble in the organic dye liquor, but which do not solubilise the dyestuffs. The following, for example, may be mentioned as particularly suitable dispersing agents: oxazolines, cellulose derivatives, higher fatty acids, salts of higher fatty acids, e.g. cobalt stearate, aluminium tripalmitate; high-molecular condensation products of polypropylene with ethylene oxide having molecular weights of 500 to 7000, or polywaxes, e.g. Pluronic P 104 (Fa. Wyandotte USA), molecular weight ca. 5500; addition products of alkylene oxides, particularly ethylene oxide, with higher fatty acids, fatty amides, aliphatic alcohols, mercaptans or amines with alkyl phenols of which the alkyl radicals contain at least 7 carbon atoms; esters of polyalcohols, especially monoor diglycerides of fatty acids, e.g. the monoglycerides of lauric, stearic, palmitic or oleic acid, as well as fatty acid esters of sugar alcohols, such as of sorbitol, sorbitans and saccharose, e.g. sorbitan monolaurate (Span 20), -palmitate (Span 40), -stearate (Span 60), -oleate (Span -sesquioleate, -trioleate (Span or their oxethylation products; and, finally, also quaternary ammonium salts such as dodecylammonium acetate, cetylpyridinium acetate, or quaternated alkylammonium polyglycol ethers such as are described in the Swiss Pat. Specification No. 409,94l, Sapamines such as Sapamine CH, KW, MS or DC, polydiene resins, fatty acid amides, or substances which contain the amide groups in ring form, such as in the case of the derivatives of polyvinylpyrrolidone, that are obtainable commercially, e.g. under the name of Antaron V 216 and V 220," and have a molecular weight of about 7000 to 9000.

The organic dye liquor according to the invention can contain as further additives dispersing agents such as the above mentioned, or acids such as formic acid or glacial acetic acid.

The organic dye liquors according to the invention are suitable for the dyeing of synthetic organic material of the most diverse kinds of processes known per se. Examples of such materials are: fibre materials made from synthetic polyamide, such as condensation products from hexamethylenediamine and adipic acid (polyamide 6.6) or sebacic acid (polyamide 6.10), or mixed condensation products, e.g. from hexamethylenediamine, adipic acid and e-caprolactam (polyamide 6.6/6), also polymerisation products from e-caprolactam, known under the trade-name of Polyamide 6," Perlon, Grilon" or Enkalon," or from m-aminoundecanoic acid, Polyamide 11" or Rilsan.

Also mentioned are: acid modified synthetic fibres such as acid modified polyamide, polyurethane and polyester fibres, and particularly polyacrylonitrile or polyacrylonitrile copolymer fibres. With the use of polyacrylonitrile copolymer fibres, the acrylonitrile proportion is preferably at least 80 per cent by weight of the copolymer. As comonomers, there are used, besides acrylonitrile, normally other vinyl compounds, e.g. vinylidine chloride, vinylidene cyanide, vinyl chloride, methacrylate, methylvinylpyridine, N-vinylpyrrolidone, vinyl acetate, vinyl alcohol or styrenesulphonic acid, or polyolefin fibres such as Polycrest."

Particularly applicable, however, are cellulose-2 -and -triacetate, but especially polyester materials such as linear high-molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols, e.g. those from terephthalic acid and ethylene glycol or dimethylolcyclohexane, and mixed polymers from terephthalic acid and isophthalic acid and ethylene glycol.

Also mixtures of the mentioned fibres can be used, particularly mixtures of synthetic polyamide and polyester fibres.

The process according to the invention, which is preferably carried out in closed, pressure-tight apparatus, e.g. in circulation apparatus, jet-machines, winchdyeing machines, drum-type dyeing machines, vats, paddle-dyeing machines and cheese dyeing apparatus, can be carried out, for example, as follows: The material to be dyed is placed into the organic dye bath at room temperature, with a ratio of material to liquor of 1:3 to 1:40, preferably 1:5 to 1:20; the finely dispersed dyestufi is added to the liquor; and the dye bath is then, heated to above 100C, advantageously to between 120 and 150C, and held at this temperature for ca. 5 to 120 minutes, advantageously for to 45 minutes. After attainment of the desired depth of colour, or with complete exhaustion of the dye bath, the bath is cooled; the dyed material removed from the bath; and, optionally after rinsing, e.g. by treatment twice with perchloroethylene for 5 minutes at 85C, dried, advantageously in vacuo with saturated steam for ca. 10 minutes.

The use of organic dye liquors instead of water as the dye bath offers a number of advantages: in the solventexhaust process, the exhaustion of the dye bath occurs more quickly than in aqueous media, resulting in shorter dyeing times; furthermore, the organic dye liquor can be easily recovered, e.g. by passage through an activecharcoal filter, in consequence of which the ever increasing difficulties associated with the cleansing of effluent are completely avoided. The purified recovered dye liquors can be used afresh as organic dye liquors to an unlimited extent. By application of a process according to the invention, it is moreover possible, provided that suitable equipment is available, to dye in excellent dye yield, in a gentle manner and without accumulation of contaminated water, synthetic organic material in the most varied stages of processing, e.g. in the form of flock, slubbing, yarn, textured threads, fabric or knitwear. By virtue of good bath exhaustion, a reductive final cleansing of the dyed material is in most cases not necessary. On polyester in particular, dyeings are obtained which have good fastness to sublimation together with a satisfactory equalization of differences in affinity arising from the material, without the physical properties of the fibres being impaired.

The following examples serve to illustrate the invention. The temperatures are expressed in degrees Centigrade. Where otherwise not described in the examples, either chemically pure (=stabiliser-free) tetrachloroethylene is used, or tetrachloroethylene to which has been added stabilisers other than aliphatic, cycloaliphatic, aromatic or heterocyclic amines.

EXAMPLE 1 An amount of 0.1 g of the dyestuff of the formula is dissolved in 32 g 20 ml) of tetrachloroethylene at The warm dyestuff solution and 10 g of textured polyethylene glycol terephthalate knitted fabric are placed into a closable dyeing apparatus, which is designed to enable movement of the textile material to be effected and which contains 64 g 80 ml) of paraffin oil heated to 80. The apparatus is then closed and, with continuous movement of the textile material, the bath temperature raised within 10 minutes to 140, and this temperature maintained for 30 minutes. After cooling to 80, the dyed knitwear is removed, and squeezed out to leave as little residual liquor as possible in the material; it is subsequently rinsed twice by being heated with tetrachloroethylene, with a material to liquor ratio of 1:8, in the above mentioned apparatus for 5 minutes at the material is afterwards squeezed out and finally dried azeotropically with aqueous saturated steam for 30 minutes.

There is obtained in this manner on textured polyethylene glycol terephthalate knitted fabric free from tetrachloroethylene a deeply coloured, even orange dyeing which is well dyed throughout and which has very good fastness to dry and to wet processing.

if, instead of the dyestuff used in Example 1, 0.1 g of one of the dyestuffs listed in the following Table 1, Column I1, is used, with otherwise the same procedure as that described in the example, then dyeings on textured polyester material are obtained in the shades given in Column 111.

Table I I II III Example Dyestuff Shade on No. polyester N I) H c N .i 2 N@- j\ A brilliant HSCLI yellow Cl j OCH i 0,.N N=N-CH c=0 llow \IC N/ O CH,

4 R H (ca. 50%) and SO NCH CH OR cocH, (ca. 50%) /CH 5 H C N=N-fi(fl yellow N HO H /C H,CN 6 O,N N=N N\ red OH O NH,

7 Br blue NH, 0 on EXAMPLE 8 0.012 g of Antaron V 2l6 and 0.l28 g of paraffin oil, in 64 g ml) of tetrachloroethylene, heating of the dispersion to 60, and subsequent addition thereof to 48 g 60 ml) of paraffin oil at 60. The dyeing apparatus is then closed, and the dye bath heated, with continuous movement of the material being dyed, within 10 minutes to 140C, and maintained at this temperature for 30 minutes. After cooling to the dyed yarn is removed, squeezed out, and then rinsed in the manner described in Example I and finally dried.

There is obtained in this manner on polyethylene glycol terephthalate yarn free from tetrachloroethylene a deeply coloured red dyeing having fastness to wet processing, to sublimation and to rubbing. The residual dye liquor is practically colourless.

If the same amount of heavy petrol, kerosene or Dekalin is used instead of paraffin oil, the procedure being otherwise as described in Example 8, then there EXAMPLE 9 If there is used, instead of the stock dispersion given in Example 8, 0.54 g of a stock dispersion containing 0.08 g of the dyestuff of the formula cmcmon R H (ca. 70%) and CH,CH,SCH,CH,OH (ca. 30%) 0.08 g of Antaron V 216 and 0.38 g of paraffin oil, the procedure being otherwise as described in Example 8, then there is obtained on polyethylene glycol terephthalate yarn a deeply coloured blue dyeing which is well dyed throughout and which is fast to light, to wet processing and to sublimation. The residual dye liquor is practically colourless.

The stock dispersion employed in the example was produced as described in Example 8, but with the use of 15 g of the dyestuff of the formula given in Example 9, 15 g of Antaron V 216 and 70 g of paraffin oil.

EXAMPLE 10 10 g of textured polyethylene glycol terephthalate fabric (TREVlRA) is placed, with a material to liquor ratio of 1:10, into a dye bath at 60 contained in a closable dyeing apparatus, the said dye bath having been 10 prepared by dispersion of 0.22 g of the stock dispersion containing 0.03 g of the dyestuff of the formula 0.006 g of Pluronic P 104 and 0.184 g of paraffin oil, and 0.27 g of the stock dispersion given in Example 9, in 58 g 40 ml) of trichloroethylene, heating of the dispersion to 60 and subsequent addition thereof to 48 g 60 ml) of paraffin oil at 60. The dyeing apparatus is then closed and, with continuous movement of the material being dyed, the temperature of the dye bath raised within 5 minutes to 140 and this temperature maintained for 30 minutes. After cooling to 80, the dyed fabric is removed and squeezed out; it is then rinsed twice by being heated with trichloroethylene, with a material to liquor ratio of 1:10, in the above mentioned apparatus for 5 minutes at squeezed out, and afterwards azeotropically dried with aqueous saturated steam for 15 minutes.

There is obtained in this manner on textured polyethylene glycol terephthalate fabric free from trichloroethylene a deeply coloured, even green dyeing which is excellently well dyed throughout, and which has very good fastness to wet processing, to sublimation and to light. The residual dye liquor is practically colourless.

The stock dispersion of the formula given in the example was produced in the manner described in Example 8, but with employment of 15 g of the dyestuff of the above formula, 3 g of Pluronic P 104 (a polyoxypropylenepolyoxyethylene compound, mol. weight 2500) and 82 g of paraffin oil.

If there is used, instead of the dyestuff mixture employed in Example 10, 0.1 g of one of the undiluted dyestuffs listed in the following Table 11, Column 11, added as a l0 percent stock dispersion, the procedure otherwise being as described in Example 10, then on textured polyester material there are obtained dyeings in the shades described in Column ll].

TABLE 1] I ll Examp. Dyestuff Shade H C 1 11 yellow N=N 0H oso cn.

c I H,C N 12 HO-CJLO -\N=N on yellow N /CN 13 (HOCH,CHCH1)2N CH=C yellow CN 0H /CN 14 (H0H4Cz}gN CH=C\ yellow CN CH3 HO 0 NH:

SCH,CHCH,OH 15 blue TABLE ll-continued' I II III Examp. Dyestuff Shade Not 27 blue scmcmon /C,HOH

| \C2H40H blue 28 c yC\ 0 OH N=N N/ I i I \CJLOH bl 29 C ue c. OH N=N- N/ i 4 30 l moH blue /s NHCOCl-l N /C2H,OH clcn cumnqs- N= N\ red Ill C,H,0H

CI CH3 ocHa cnou 2 'l 32 T41 \H b] C ue 00cm,

CHOH N=N N 2 4 v I C- .H4OH reddish- 33 C blue EXAMPLE 34 v EXAMPLE 35 If 10 g of a fabric made from cellulose-2 rs-acetate is used instead of the polyethylene glycol terephthalate yarn described in Example 8, with the'procedure otherwise as described in Example 8, then there is obtained on the cellulose-2 r-z=lcetate fabri'c a deeply coloured even red dyeing well dyed throughout and possessing good fastness to wet processing and to light. The resid- 65 ual dye liquor is practically colourless.

scribed in Example 8, the procedure otherwise being as described in Example 8, then there is obtained on the cellulose triacetate fabric a deeply coloured, even red dyeing which is well dyed throughout, and which has good fastness to wet processing and to light.

EXAMPLE 36 An amount of 0.22 g of the stock dispersion of the formula given in Example is dispersed in 32 g 20 ml) of tetrachloroethylene; the dispersion is heated to 60 and then added to 64 g 80 ml) of paraffin oil at 60 contained in a closable dyeing apparatus. There is then introduced into the dye liquor 10 g of a polyamide-6.6-tricot; the dyeing apparatus is closed and the dye bath heated, with continuous movement of the material being dyed, within 5 minutes to 140, and this temperature maintained for 30 minutes. After cooling to 80, the dyed material is removed and squeezed out; it is rinsed twice by being heated with tetrachloroethylene in the dyeing apparatus, with a material to liquor ratio of 1:10, for 5 minutes at 50, and subsequently azeotropically dried with aqueous saturated steam for minutes.

There is obtained in this manner on polyamide-6.6- tricot a deeply coloured, even yellow dyeing which is free from perchloroethylene.

EXAMPLE 37 If 10 g of polyacrylonitrile fabric are used instead of the polyamide-6.6-tricot mentioned in Example 36, with the procedure otherwise as described in Example 36, then there is obtained on the said polyacrylonitrile fabric a deeply coloured, even yellow dyeing.

EXAMPLE 38 An amount of 10 g of textured polyethylene glycol terephthalate knitted fabric is placed into a bath (ratio of material to liquor 1:10) contained in a closable dyeing apparatus, the said bath having been prepared by the dispersion of 0. l 5 g of a stock dispersion consisting of 0.012 g of Antaron V 216 (modified polyvinylpyrrolidone), 0.128 g of paraffin oil and 0.01 g of 2,6-di-tert- .butylphenol in 32 g ml) of commercial tetrachloroethylene stabilised with an aliphatic, cycloaliphatic, aromatic or heterocyclic amine.

The temperature is raised to 60; an addition is made of 64 g 80 ml) of paraffin oil at 60, the dyeing apparatus is closed and, with continual movement of the material to be treated, the bath heated within 10 minutes to 140 and this temperature maintained for 30 minutes.

After cooling to 80, the thus treated knitted fabric is removed and squeezed out to leave as little residual liquor as possible in the material; it is then rinsed twice by being heated with tetrachloroethylene, in the ratio of material to liquor of I :8, in the above mentioned apparatus for 5 minutes at 85, squeezed out, and subsequently azeotropically dried with aqueous saturated steam for 30 minutes.

The polyethylene glycol terephthalate knitted fabric treated in this manner displays absolutely no grey discolouration or modification of its fibre-physical properties compared with an untreated comparative sample. Similar results are obtained if, instead of 2,6-di-tert- .butylphenol, other oxidation-inhibitors are employed, such as, e.g. 4-tert.butylphenol, 2,6-di-tert.butyl-4- methylphenol or their alkoxy derivatives, such as, for

example, 2-tert.butyl-4-methoxyphenol or 3-tert.butyl-' 4-methoxyphenol, or mixtures of these compounds with each other.

Without the addition of 2,6-di-tert.butylphenol or of the oxidation-inhibitors mentioned in the example, there occurs a severe grey discolouration of the treated 16 polyethylene glycol terephthalate knitted fabric, compared with the result obtained in the'comparative case where the knitted fabric has not been treated.

EXAMPLE 39 An amount of 10 g of polyethylene glycol terephthalate fabric (TREVlRA) is placed into a bath (ratio of material to liquor 1:10) contained in a closable dyeing apparatus, the said bath having been prepared by the dispersion of 0. 1 71 g of a stock dispersion consisting of 0.012 g ofAntaron V 216, 0.128 g ofparaffin oil, 0,001 g of hydroquinone and 0.03 g of the finely dispersed dyestuff in 32 g 20 ml) of commercial tetrachloroethylene stabilised with an aliphatic, cycloaliphatic, aromatic or heterocyclic amine.

The temperature is raised to 60 and an addition then made of 64 g ml) of paraffin oil, the procedure being otherwise as described in Example 38. There is obtained in this manner, on tetrachloroethylene-free polyethylene glycol terephthalate fabric, a pure, deeplycoloured yellow dyeing which is wetfast and fast to sublimation and rubbing and which corresponds to an equivalent dyeing in pure perchloroethylene without the addition of 0.001 g of hydroquinone as anti-oxidant.

1f the procedure is carried out as described in the example, but without the addition of 0.001 g of hydroquinone, then a severely dulled, unserviceable yellow dyeing results.

lf in the above example there is used, instead of the employed hydroquinone, its monoor dialkyl ether, such as, e.g. hydroquinonemonobutyl ether or methylhydroquinone-n-butyl ether, in amounts of 0.001 to 0.01 g, then likewise there are obtained pure yellow dyeings exhibiting no grey discolouration or dulling,

With the use of tetrachloroethylene to which has been added stabilisers other than aliphatic, cycloaliphatic, aromatic or heterocyclic amines, there occurs, without addition of the given stabilisers, likewise no grey discolouration, or modification of the fibre-physical properties of the treated material, in comparison with the result obtained on an untreated comparative sample.

We claim:

1. A process for the exhaust dyeing of synthetic organic materiaL'the process comprising the step of contacting the synthetic organic material, at a temperature above C, with a dye liquor consisting essentially of 20 to 75 percent by weight of a water-insoluble, aliphatic or cycloaliphatic hydrocarbon having 8 to 25 carbon atoms, and 80 to 25 percent by weight of a polyhalogenated, lower aliphatic hydrocarbon boiling between 70 and 180C, and at least one finely-divided dispersion dyestuff which is difficutly soluble in boiling perchloroethylene.

2. The process of claim 1, wherein the dyeing is performed at a temperature above C.

3. The process of claim 1, wherein there is used a water-insoluble, aliphatic hydrocarbon having 12 to 25 carbon atoms.

4. The process of claim 1, wherein the waterinsoluble, aliphatic hydrocarbon is heavy petrol, kerosene or paraffin oil.

5. The process of claim 4, wherein the waterinsoluble, aliphatic hydrocarbon is paraffin oil.

6. The process of claim 1, wherein the polyhalogenated, lower aliphatic hydrocarbon is chlorinated hydrocarbon boiling between 80 and 130C.

7. The process of claim 6, wherein the polyhalogenated, lower aliphatic hydrocarbon is trichloroethylene, l,l,1-trichloroethane or tetrachloroethylene (perchloroethylene).

8. The process of claim I, wherein, when tetrachloroethylene stabilised with aliphatic, cycloaliphatic, aromatic or heterocyclic amines is employed, and a small amount of anti-oxidant is added to the dyebath.

9. The process of claim 8, wherein the antioxidant is employed in an amount of 0.001 to 5 g per liter of dye liquor.

10. The process of claim 8, wherein the antioxidant is selected from the class consisting of a. the derivatives of alkylated, arylated or mixed phenols, phenol ethers of phenol esters, as well as bisphenols with or without alkylene bridging, particularly those of the general formula OH HO wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl or an alkylaryl group, and n denotes the numbers to 6;

b. hydroquinone and its functional derivatives, such as hydroquinone-mono and dialkyl or arylalkyl ethers;

c. the esters of gallic acid or citraconic acid, as well as mixtures thereof;

d. dialkylphosphonates, particularly those with stearically inhibited phenols, or also p-hydroxyphenyl-phosphonates and compounds of pphenylenediamine or of p-aminophenol;

e. organic sulphur compounds having an oxidationinhibiting action, and

18 f. compounds of the formamidinesulphinic acid type or inorganic complex hydrides such as NaBl-l etc., of which the hydrogen can be partially replaced by organic radicals, such as NaBl-KOCHQ, or NaBH- 2 s)a- 11. The process of claim 1, wherein the aliphatic or cycloaliphatic hydrocarbon is present to the extent of 50 to percent by weight and the polyhalogenated, lower aliphatic hydrocarbon is present to the extent of 50 to 30 percent by weight.

12. The process of claim I, wherein the dispersion dyestuff is selected from metalfree monoand disazo dyestuffs, nitro dyestuffs, methine dyestuffs and anthraquinone dyestuffs.

13. The process of claim I, wherein the dispersion dyestuff contains a nonionic dispersing agent which is soluble in polyhalogenated, lower aliphatic hydrocarbon, but which does not solubilise the dispersion dyestuff.

14. The process of claim I, wherein the dispersion dyestuff has a solubility in boiling perchloroethylene of at most 0.05 percent by weight, and which has a particle size of at most 5 p" 15. The process of claim 1, wherein the synthetic organic material is polyester, polyamide or polyacrylonitrile fibre material.

16. The process of claim 1, wherein the synthetic organic material is fibre material made from linear, highmolecular esters of aromatic polycarboxylic acids with polyfunctional alcohols.

17. The process of claim 1, wherein the synthetic organic material is polyethylene glycol terephthalate fibre material.

18. The process of claim 1, further comprising the steps of rinsing the dyed material with a polyhalogenated, lower aliphatic hydrocarbon and drying the rinsed material.

19. A dye liquor for the dyeing of synthetic organic material, the dye liquor consisting essentially of a finely-divided dispersion dyestuff, 5 to percent by weight of a water-insoluble, aliphatic or cycloaliphatic hydrocarbon having 8 to 25 carbon atoms, and 95 to 5 percent by weight of a polyhalogenated, lower aliphatic hydrocarbon boiling between 70 and C.

20. The dye liquor of claim 19, wherein the aliphatic or cycloaliphatic hydrocarbon is present to the extent of 10 to 70 percent by weight and the polyhalogenated, lower aliphatic hydrocarbon is present to the extent of 90 to 30 percent by weight. 

1. A PROCESS FOR THE EXHAUST DYEING OF SYNTHETIC ORGANIC MATERIAL, THE PROCESS COMPRISING THE STEP OF CONTACTING THE SYNTHETIC ORGANIC MATERIAL, AT A TEMPRATURE ABOVE 100*C, WITH A DYE LIQUOR CONSISTING ESSENTIALLY OF 20 TO 75 PERCENT BY WEIGHT OF A WATER-INSOLUBLE, ALIPHATIC OR CYCLOALIPHATIC HYDROCARBON HAVING 8 TO 25 CARBONS ATOMS, AND 80 TO 25 PERCENT BY WEIGHT OF A POLYHALOGENATED, LOWR ALIPHATIC HYDROCARBON BOILING BETWEN 70* AND 180*C, AND AT LEAST ONE FINELY-DIVIDED DISPERSION DYESTUFF WHICH IS DIFFICUTLY SOLUBLE IN BOILINGPECHLOROETHYLENE.
 2. The process of claim 1, wherein the dyeing is performed at a temperature above 120*C.
 3. The process of claim 1, wherein there is used a water-insoluble, aliphatic hydrocarbon having 12 to 25 carbon atoms.
 4. The process of claim 1, wherein the waterinsoluble, aliphatic hydrocarbon is heavy petrol, kerosene or paraffin oil.
 5. The process of claim 4, wherein the waterinsoluble, aliphatic hydrocarbon is paraffin oil.
 6. The process of claim 1, wherein the polyhalogenated, lower aliphatic hydrocarbon is chlorinated hydrocarbon boiling between 80* and 130*C.
 7. The process of claim 6, wherein the polyhalogenated, lower aliphatic hydrocarbon is trichloroethylene, 1,1,1-trichloroethane or tetrachloroethylene (perchloroethylene).
 8. The process of claim 1, wherein, when tetrachloroethylene stabilised with aliphatic, cycloaliphatic, aromatic or heterocyclic amines is employed, and a small amount of anti-oxidant is added to the dye bath.
 9. The process of claim 8, wherein the antioxidant is employed in an amount of 0.001 to 5 g per liter of dye liquor.
 10. The process of claim 8, wherein the antioxidant is selected from the class consisting of a. the derivatives of alkylated, arylated or mixed phenols, phenol ethers of phenol esters, as well as bisphenols with or without alkylene bridging, particularly those of the general formula
 11. The process of claim 1, wherein the aliphatic or cycloaliphatic hydrocarbon is present to the extent of 50 to 70 percent by weight and the polyhalogenated, lower aliphatic hydrocarbon is present to the extent of 50 to 30 percent by weight.
 12. The process of claim 1, wherein the dispersion dyestuff is selected from metal-free mono- and disazo dyestuffs, nitro dyestuffs, methine dyestuffs and anthraquinone dyestuffs.
 13. The process of claim 1, wherein the dispersion dyestuff contains a nonionic dispersing agent which is soluble in polyhalogenated, lower aliphatic hydrocarbon, but which does not solubilise the dispersion dyestuff.
 14. The process of claim 1, wherein the dispersion dyestuff has a solubility in boiling perchloroeThylene of at most 0.05 percent by weight, and which has a particle size of at most 5 Mu .
 15. The process of claim 1, wherein the synthetic organic material is polyester, polyamide or polyacrylonitrile fibre material.
 16. The process of claim 1, wherein the synthetic organic material is fibre material made from linear, high-molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols.
 17. The process of claim 1, wherein the synthetic organic material is polyethylene glycol terephthalate fibre material.
 18. The process of claim 1, further comprising the steps of rinsing the dyed material with a polyhalogenated, lower aliphatic hydrocarbon and drying the rinsed material.
 19. A dye liquor for the dyeing of synthetic organic material, the dye liquor consisting essentially of a finely-divided dispersion dyestuff, 5 to 95 percent by weight of a water-insoluble, aliphatic or cycloaliphatic hydrocarbon having 8 to 25 carbon atoms, and 95 to 5 percent by weight of a polyhalogenated, lower aliphatic hydrocarbon boiling between 70* and 180*C.
 20. The dye liquor of claim 19, wherein the aliphatic or cycloaliphatic hydrocarbon is present to the extent of 10 to 70 percent by weight and the polyhalogenated, lower aliphatic hydrocarbon is present to the extent of 90 to 30 percent by weight. 